CN110841598A - Preparation method and application of synthetic metal organic framework adsorbent - Google Patents
Preparation method and application of synthetic metal organic framework adsorbent Download PDFInfo
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- CN110841598A CN110841598A CN201911118270.1A CN201911118270A CN110841598A CN 110841598 A CN110841598 A CN 110841598A CN 201911118270 A CN201911118270 A CN 201911118270A CN 110841598 A CN110841598 A CN 110841598A
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 51
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000010931 gold Substances 0.000 claims abstract description 34
- 229910052737 gold Inorganic materials 0.000 claims abstract description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- -1 gold ions Chemical class 0.000 abstract description 26
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000003929 acidic solution Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 6
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Polymers & Plastics (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
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- Analytical Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a preparation method and application of a synthetic metal organic framework adsorbent, belonging to the technical field of nano material preparation. Mixing zirconium tetrachloride and trithiocyanuric acid, adding DMF (dimethyl formamide) and hydrochloric acid at room temperature, mixing for 2-4 h, heating to 130-135 ℃, keeping for 24-28 h, filtering, washing the formed precipitate with DMF, and drying to obtain the synthetic metal organic framework adsorbent. The synthetic metal organic framework adsorbent can adsorb gold ions in an acidic solution, is low in material cost, simple in process preparation, easy to separate from an aqueous solution, high in adsorbability and reusable.
Description
Technical Field
The invention relates to a preparation method and application of a synthetic metal organic framework adsorbent, belonging to the technical field of nano material preparation.
Background
Gold plays an irreplaceable role in many industrial productions and daily lives, with many excellent physicochemical properties, such as the electronics industry, medical instruments, aerospace, electronic communications, chemical production and jewelry. However, industrial activities generate large amounts of gold-containing waste water, resulting in the loss of large amounts of gold.
Methods for recovering gold ions from aqueous solutions can be broadly classified into adsorption methods, solvent extraction methods, displacement precipitation methods, ion exchange methods, electrolytic methods, and the like. Wherein, the adsorption is a new means which is beneficial to the recovery of gold ions in the aqueous solution due to simple operation process, high efficiency and low cost. Through recent research and development, adsorbent types can be broadly classified into ion exchange resins, activated carbons and nanocomposites, chitosan, clays, zeolites, chelating resins and MCM-41. The Metal Organic Framework (MOF) has been developed rapidly in recent years as a new material adsorbent. The large specific surface area, the plurality of active sites and the adjustable pore size of the adsorbent make the adsorbent have wide prospects in the adsorption field. However, some existing MOF adsorbents have low selectivity. To increase the adsorption selectivity and capacity of MOFs, complex post-modifications are often required. Therefore, it is important to prepare novel MOFs with high selectivity and adsorption capacity by a simple process.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention provides a preparation method and application of a synthetic metal organic framework adsorbent. The synthetic metal organic framework adsorbent can adsorb gold ions in an acidic solution, is low in material cost, simple in process preparation, easy to separate from an aqueous solution, high in adsorbability and reusable. The invention is realized by the following technical scheme.
A preparation method of a synthetic metal organic framework adsorbent comprises the following specific steps:
mixing zirconium tetrachloride and trithiocyanuric acid, adding DMF (dimethyl formamide) and hydrochloric acid at room temperature, mixing for 2-4 h, heating to 130-135 ℃, keeping for 24-28 h, filtering, washing the formed precipitate with DMF, and drying to obtain the synthetic metal organic framework adsorbent.
The molar ratio of the zirconium tetrachloride to the trithiocyanuric acid is 1-3: 1-2.
The concentration of the hydrochloric acid is 10-15 mol/L, and the volume ratio of DMF to hydrochloric acid is 10-11: 1-3.
The volume ratio of the trithiocyanuric acid to the DMF is 1-3: 10-12.
The metal organic framework adsorbent prepared by the preparation method of the synthetic metal organic framework adsorbent can be applied to adsorption and separation of gold in acidic leaching solution.
The invention has the beneficial effects that:
(1) the MOF adsorbent prepared by the invention is mainly used for adsorbing and separating gold ions from an acid leaching solution, and has higher adsorption capacity to the gold ions.
(2) The preparation method is simple and convenient, has low cost and good application and economic value.
(3) The MOF adsorbent disclosed by the invention is non-toxic and harmless, stable in performance, easy to separate, reusable and free of secondary pollution to the environment.
In conclusion, the MOF adsorbent for adsorbing and separating gold has a great potential in the aspect of adsorbing and separating gold ions.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1
The preparation method of the synthetic metal organic framework adsorbent comprises the following specific steps:
mixing zirconium tetrachloride and trithiocyanuric acid, adding DMF and hydrochloric acid at room temperature, mixing for 2h, heating to 130 ℃ and keeping for 24h, filtering, washing the formed precipitate with DMF, and drying to obtain a synthetic metal organic framework adsorbent, which is defined as ZT-MOF; wherein the molar ratio of the zirconium tetrachloride to the trithiocyanuric acid is 1: 1; the concentration of hydrochloric acid is 10mol/L, and the volume ratio of DMF to hydrochloric acid is 10: 1; the volume ratio of the trithiocyanuric acid to the DMF is 1: 10.
And (3) testing the performance of adsorbing gold ions:
10mgZT-MOF adsorbent is put into a gold ion solution with the initial concentration of 100mg/L for shaking adsorption for 3h, the adsorbent is centrifugally separated, the concentration of the residual gold ions in the filtrate is determined to be 13.8mg/L by ICP-OES, and the adsorption rate is 86.2%. The adsorbent having adsorbed gold ions was washed in a thiourea solution (8 wt%) for 12 hours with stirring, then washed 5 times with distilled water, and finally dried in vacuum at 60 ℃ for 12 hours. 10mg of the adsorbent is put into a gold ion solution with the initial concentration of 100mg/L for shaking adsorption for 3 hours, the adsorbent is centrifugally separated, the concentration of the residual gold ions in the filtrate is measured by ICP-OES to be 14.3mg/L, and the adsorption rate is 85.7%. The MOF adsorbent ZT-MOF for adsorbing and separating gold can be recycled.
Example 2
The preparation method of the synthetic metal organic framework adsorbent comprises the following specific steps:
mixing zirconium tetrachloride and trithiocyanuric acid, adding DMF and hydrochloric acid at room temperature, mixing for 4h, heating to 135 deg.C, maintaining for 28h, filtering, washing the precipitate with DMF, and drying to obtain synthetic metal organic framework adsorbent, defined as ZT-MOF; wherein the molar ratio of the zirconium tetrachloride to the trithiocyanuric acid is 1: 2; the concentration of hydrochloric acid is 12mol/L, and the volume ratio of DMF to hydrochloric acid is 11: 3; the volume ratio of the trithiocyanuric acid to the DMF is 3: 12.
And (3) testing the performance of adsorbing gold ions:
and putting 10mgZT-MOF adsorbent into a gold ion solution with the initial concentration of 100mg/L, performing vibration adsorption for 3h, centrifuging to separate the adsorbent, and measuring the concentration of the residual gold ions in the filtrate to be 25.1mg/L by using ICP-OES, wherein the adsorption rate is 74.9%. The adsorbent having adsorbed gold ions was washed in a thiourea solution (10 wt%) for 5 hours with stirring, then washed 5 times with distilled water, and finally dried in vacuum at 60 ℃ for 12 hours. 10mg of the adsorbent is put into a gold ion solution with the initial concentration of 100mg/L for shaking adsorption for 3 hours, the adsorbent is centrifugally separated, the concentration of the residual gold ions in the filtrate is measured by ICP-OES to be 24.8mg/L, and the adsorption rate is 75.2%. The MOF adsorbent ZT-MOF for adsorbing and separating gold can be recycled.
Example 3
The preparation method of the synthetic metal organic framework adsorbent comprises the following specific steps:
mixing zirconium tetrachloride and trithiocyanuric acid, adding DMF and hydrochloric acid at room temperature, mixing for 3h, heating to 132 ℃ and keeping for 25h, filtering, washing the formed precipitate with DMF, and drying to obtain a synthetic metal organic framework adsorbent, which is defined as ZT-MOF; wherein the molar ratio of the zirconium tetrachloride to the trithiocyanuric acid is 3: 2; the concentration of hydrochloric acid is 15mol/L, and the volume ratio of DMF to hydrochloric acid is 10: 2; the volume ratio of the trithiocyanuric acid to the DMF is 2: 11.
And (3) testing the performance of adsorbing gold ions:
10mgZT-MOF adsorbent is put into a gold ion solution with the initial concentration of 100mg/L for shaking adsorption for 3h, the adsorbent is centrifugally separated, the concentration of the residual gold ions in the filtrate is determined to be 26.3mg/L by ICP-OES, and the adsorption rate is 73.7%. The adsorbent having adsorbed gold ions was washed in a thiourea solution (9 wt%) for 6 hours with stirring, then washed 5 times with distilled water, and finally dried in vacuo at 60 ℃ for 12 hours. 10mg of the adsorbent is put into a gold ion solution with the initial concentration of 100mg/L for shaking adsorption for 3 hours, the adsorbent is centrifugally separated, the concentration of the residual gold ions in the filtrate is measured by ICP-OES to be 25.9mg/L, and the adsorption rate is 74.1%. The MOF adsorbent ZT-MOF for adsorbing and separating gold can be recycled.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (5)
1. A preparation method of a synthetic metal organic framework adsorbent is characterized by comprising the following specific steps:
mixing zirconium tetrachloride and trithiocyanuric acid, adding DMF (dimethyl formamide) and hydrochloric acid at room temperature, mixing for 2-4 h, heating to 130-135 ℃, keeping for 24-28 h, filtering, washing the formed precipitate with DMF, and drying to obtain the synthetic metal organic framework adsorbent.
2. The method of claim 1, wherein the adsorbent comprises: the molar ratio of the zirconium tetrachloride to the trithiocyanuric acid is 1-3: 1-2.
3. The method of claim 1, wherein the adsorbent comprises: the concentration of the hydrochloric acid is 10-15 mol/L, and the volume ratio of DMF to hydrochloric acid is 10-11: 1-3.
4. The method of claim 1, wherein the adsorbent comprises: the volume ratio of the trithiocyanuric acid to the DMF is 1-3: 10-12.
5. A metal organic framework adsorbent prepared by the method for preparing the synthetic metal organic framework adsorbent according to any one of claims 1 to 4, which can be applied to adsorption separation of gold in acidic leachate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911118270.1A CN110841598A (en) | 2019-11-15 | 2019-11-15 | Preparation method and application of synthetic metal organic framework adsorbent |
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| CN201911118270.1A CN110841598A (en) | 2019-11-15 | 2019-11-15 | Preparation method and application of synthetic metal organic framework adsorbent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680601A (en) * | 2020-12-02 | 2021-04-20 | 昆山鸿福泰环保科技有限公司 | Method for recovering silver and gold from silver and gold-containing anode slime |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108160049A (en) * | 2018-01-08 | 2018-06-15 | 昆明理工大学 | It is a kind of to be used to adsorb modified corn shell adsorbent of gold ion and its preparation method and application |
| CN108212106A (en) * | 2018-01-08 | 2018-06-29 | 昆明理工大学 | A kind of adsorbent of thiosemicarbazide modified corn shell and its preparation method and application |
-
2019
- 2019-11-15 CN CN201911118270.1A patent/CN110841598A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108160049A (en) * | 2018-01-08 | 2018-06-15 | 昆明理工大学 | It is a kind of to be used to adsorb modified corn shell adsorbent of gold ion and its preparation method and application |
| CN108212106A (en) * | 2018-01-08 | 2018-06-29 | 昆明理工大学 | A kind of adsorbent of thiosemicarbazide modified corn shell and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| ZHEN HUANG等: "Selective recovery of gold ions in aqueous solutions by a novel trithiocyanuric-Zr based MOFs adsorbent", 《JOURNAL OF MOLECULAR LIQUIDS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680601A (en) * | 2020-12-02 | 2021-04-20 | 昆山鸿福泰环保科技有限公司 | Method for recovering silver and gold from silver and gold-containing anode slime |
| CN112680601B (en) * | 2020-12-02 | 2022-04-15 | 昆山鸿福泰环保科技有限公司 | Method for recovering silver and gold from silver and gold-containing anode slime |
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